WO1997014821A1 - Ajustement du poids de couche dans des systemes de phosphatation acceleres a l'hydroxylamine - Google Patents

Ajustement du poids de couche dans des systemes de phosphatation acceleres a l'hydroxylamine Download PDF

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Publication number
WO1997014821A1
WO1997014821A1 PCT/EP1996/004374 EP9604374W WO9714821A1 WO 1997014821 A1 WO1997014821 A1 WO 1997014821A1 EP 9604374 W EP9604374 W EP 9604374W WO 9714821 A1 WO9714821 A1 WO 9714821A1
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WO
WIPO (PCT)
Prior art keywords
phosphating
ions
acid
hydroxylamine
free
Prior art date
Application number
PCT/EP1996/004374
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German (de)
English (en)
Inventor
Jan-Willem Brouwer
Jürgen Geke
Peter Kuhm
Frank-Oliver Pilarek
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU72879/96A priority Critical patent/AU7287996A/en
Publication of WO1997014821A1 publication Critical patent/WO1997014821A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates

Definitions

  • the invention relates to a method for controlling the layer weight in the phosphating of metal surfaces with aqueous, acidic phosphating solutions which contain zinc and phosphate ions and hydroxylamine in free or bound form, and to their use as pretreatment of the metal surfaces for a subsequent coating , especially an electro dip painting.
  • the method is applicable for the treatment of surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy aluminized steel.
  • the phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers on the metal surface, which in themselves improve corrosion resistance and, in conjunction with lacquers and other organic coatings, to a substantial increase in adhesion and resistance to migration under corrosion contribute.
  • Such phosphating processes have long been known in the prior art.
  • the Low-zinc phosphating processes in which the phosphating solutions have comparatively low contents of zinc ions of e.g. B. 0.5 to 2 g / 1.
  • An important parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range> 12 and can take values up to 30.
  • phosphate layers with significantly improved corrosion protection and paint adhesion properties can be formed.
  • z. B. 0.5 to 1.5 g / 1 manganese ions and z. B. 0.3 to 2.0 g / 1 of nickel ions as a so-called trication process for the preparation of metal surfaces for painting, for example for the cathodic electrodeposition of car bodies, widely used.
  • DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions.
  • the phosphating baths described here contain, in addition to 0.2 to 10 g / 1 nitrate ions, further oxidizing agents which act as accelerators, selected from nitrite, chlorate or an organic oxidizing agent. Concerns about the accelerators nitrite and nitrate are being raised due to the possible formation of nitrous gases.
  • the phosphating process disclosed in WO 86/04931 works without nitrates.
  • the accelerator system is based on a combination of bromate and m-nitrobenzenesulfonate. Only zinc is given as the essential polyvalent cation, and nickel, manganese or cobalt is given as further optional cations.
  • the phosphating solutions, in addition to zinc, contain at least 2 of these optional metals.
  • DE-A-40 13 483 discloses phosphating processes with which good corrosion protection properties similar to those obtained with the trication processes can be achieved. These processes do without nickel and instead use copper in low concentrations, 0.001 to 0.03 g / 1. Oxygen and / or other oxidizing agents having the same effect are used to oxidize the divalent iron formed in the pickling reaction of steel surfaces to the trivalent stage. Nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds such as nitrobenzenesulfonate are specified as such.
  • German patent application DE 42 10 513 modifies this process by adding hydroxylamine, its salts or complexes in an amount of 0.5 to 5 g / 1 hydroxylamine as a modifying agent for the morphology of the phosphate crystals formed.
  • EP-A-315 059 specifies the particular effect of the use of hydroxylamine in phosphating baths in the fact that the phosphate crystals are still formed in a desired columnar or knot-like form on steel when the zinc concentration in the phosphating bath corresponds to that for low-zinc Ver ⁇ process exceeds the usual range. This makes it possible to operate the phosphating baths with zinc concentrations of up to 2 g / 1 and with weight ratios of phosphate to zinc down to 3.7. No further statements are made about advantageous cation combinations of these phosphating baths, but nickel is used in all patent examples.
  • Nitrates and nitric acid are also used in the patent examples, even if in the description is advised against the presence of nitrate in large quantities.
  • the required hydroxylamine concentration is given as 0.5 to 50 g / 1, preferably 1 to 10 g / 1.
  • the maximum concentration of hydroxylammonium sulfate in the patent examples is 5 g / l, from which a hydroxylamine content of 2.08 g / l is calculated. (Hydroxylammonium sulfate contains 41.5% by weight of hydroxylamine).
  • the phosphating solution is sprayed onto the steel surfaces. The document does not mention the problems with immersion processes which lead to phosphate layers with significantly higher layer weights, which are undesirable as the basis for subsequent painting.
  • WO 93/03198 teaches the use of hydroxylamine as an accelerator in trication-phosphating baths with zinc contents between 0.5 and 2 g / 1 and nickel and manganese contents of 0.2 to 1.5 g / 1, respectively certain weight ratios between zinc and the other divalent cations must also be observed. Furthermore, these baths contain 1 to 2.5 g / 1 of a "hydroxylamine accelerator", which according to the description means salts of hydroxylamine, preferably hydroxylammonium sulfate. If this information is converted to free hydroxylamine, hydroxylamine contents between 0.42 and 1.04 g / l are provided. The document contains no information about the influence of different hydroxylamine concentrations on the layer weight when using the phosphating solutions in the dipping process.
  • the object of the invention is to provide a hydroxylamine-accelerated phosphating system for use in immersion processes, the desired layer weights being adjustable by the choice of a suitable accelerator concentration.
  • This object is achieved by a method for adjusting the layer weight in the phosphating of surfaces made of steel, galvanized steel, alloy-galvanized steel and aluminum and its alloys with zinc-containing phosphating solutions to values in the range from 1 to 3.5 g / m * ⁇ , characterized that the metal surfaces are immersed in a phosphating solution for a period of between one and eight minutes
  • phosphating baths In addition to zinc ions, phosphating baths generally contain sodium, potassium and / or ammonium ions to adjust the free acid.
  • free acid is familiar to those skilled in the phosphating field.
  • the method of determining free acid and total acid selected in this document is given in the example section.
  • Phosphating solutions which contain further mono- or divalent metal ions, which experience has shown to have a favorable effect on the paint adhesion and the corrosion protection of the phosphate layers produced thereby, are preferably used in the phosphating process according to the invention. Accordingly, the process according to the invention is preferably characterized in that the phosphate solution additionally contains one or more of the following cations:
  • 0.2 to 1.5 g / 1 manganese ions 0.2 to 1.5 g / 1 nickel ions, 0.02 to 1.5 g / 1, preferably 0.03 to 0.8 g / 1, and in particular 0.04 to 0.2 g / 1 cobalt ions, 0.2 to 1.5 g / 1 lithium ions , 0.2 to 2.5 g / 1 magnesium ions, 0.001 to 0.03 g / 1 copper ions.
  • the weight ratio of phosphate ions to zinc ions in the phosphate baths can vary within wide limits, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
  • the skilled worker is familiar with the free acid and total acid contents as further parameters for controlling phosphating baths. The method of determining these parameters used in this document is given in the example section. Values of the free acid between 0.3 and 1.5 points and the total acid between about 15 and about 35 points are within the technically customary range and are suitable for the purposes of this invention.
  • Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely exist as a hydroxylammonium cation due to the acidic nature of these solutions. When used as a hydroxylammonium salt, the sulfates and the phosphates are particularly suitable. In the case of the phosphates, the acid salts are preferred due to the better solubility. Hydroxylamine or its compounds are added to the phosphating bath in amounts such that the calculated concentration of the free hydroxylamine is between 1.2 and 5 g / l.
  • the phosphating baths contain hydroxylamine as the only accelerator, at most together with nitrate. Accordingly, phosphating baths which contain contain none of the other known accelerators such as, for example, nitrite, oxo anions of halogens, peroxides or nitrobenzenesulfonate.
  • nitrite oxo anions of halogens, peroxides or nitrobenzenesulfonate.
  • Phosphating baths which contain no nitrate are particularly preferred.
  • the zinc content of the phosphating bath will be set according to EP-A-315059 to values between 0.45 and 1.1 g / 1.
  • the current zinc content of the working bath is above a value of 1.1 g / l.
  • Zinc levels up to 2 g / l are harmless in the context of the present invention.
  • zinc contents of up to 2 g / l can also reduce the risk of rust formation during phosphating.
  • the form in which the cations are introduced into the phosphating baths is in principle irrelevant. It is particularly useful to use oxides and / or carbonates as the cation source.
  • the phosphating baths according to the invention preferably do not contain any substances which have an oxidizing effect on iron (II), the divalent iron changes to the trivalent state only as a result of air oxidation, so that it is called iron (III). Phosphate can precipitate. Therefore, iron (II) contents can be built up in the phosphating baths according to the invention which are significantly higher than the contents which contain baths containing oxidizing agents. In this sense, iron (II) concentrations of up to 50 ppm are normal, although values of up to 500 ppm can also occur briefly in the production process. Such iron (II) concentrations are not detrimental to the phosphating process according to the invention.
  • the phosphating baths may further contain the hardness-forming cations Mg (II) and Ca (II) in a total concentration of up to 7 nmol / l.
  • Mg (II) can also be added to the phosphating bath in amounts of up to 2.5 g / l.
  • the accelerator hydroxylamine can be slowly inactivated even if no metal parts to be phosphated are introduced into the phosphating bath. It has surprisingly been found that the inactivation of the hydroxylamine can be significantly slowed down if one or more aliphatic hydroxycarboxylic acids having 3 to 6 carbon atoms in a total amount of 0.5 to 1.5 g / l are added to the phosphating bath .
  • the hydroxycarboxylic acids are preferably selected from lactic acid, gluconic acid, tartronic acid, malic acid, tartaric acid and citric acid, citric acid being particularly preferred.
  • the temperature of the phosphating solution is preferably in the range between about 40 and about 60 ° C. It has turned out to be more positive As a side effect of the phosphating process according to the invention, it is emphasized that hydroxylamine concentrations in the amount range according to the invention significantly reduce the risk of rust formation at insufficiently flooded areas of the components to be phosphated.
  • the method according to the invention is suitable for phosphating surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel.
  • the materials mentioned can also be present side by side, as is becoming increasingly common in automobile construction.
  • Parts of the body can also consist of material that has already been pretreated, such as the Bonazink * process.
  • the base material is first chromated or phosphated and then coated with an organic resin.
  • the phosphating process according to the invention then leads to phosphating on damaged areas of this pretreatment layer or on untreated rear sides.
  • the method can be used in particular in automotive engineering, where treatment times between 1 and 8 minutes are common. It is intended in particular for the treatment of the metal surfaces mentioned before painting, in particular before cathodic electrocoating, as is customary in automobile construction.
  • the phosphating process is to be seen as a sub-step of the technically usual pretreatment chain. In this chain, the steps of cleaning / degreasing, rinsing and activating are usually preceded by the phosphating, the activation usually being carried out using activating agents containing titanium phosphate.
  • the phosphating according to the invention can be followed, if appropriate after an intermediate rinse, by a passivating aftertreatment. Chromic acid-containing ones are used for such a passivating aftertreatment Treatment baths widely used.
  • the phosphating processes and comparative processes according to the invention were checked on steel sheets (St 1405), as are used in automobile construction.
  • Phosphating with phosphating baths according to Table 1. 4 minutes of immersion at 55 ° C. In addition to the cations listed in Table 1, the phosphating baths only contained sodium ions to adjust the free acid. The baths contained no nitrite, nitrate and no oxo anions from halogens. The freshly prepared phosphating baths were stirred for 5 days at 55 ° C. before the phosphating tests were carried out, in order to observe the inactivation of the hydroxylamine. Table 1 contains the hydroxylamine concentrations of the freshly prepared phosphating baths.
  • the free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6.
  • the score is analogous of total acid consumption in ml up to a pH of 8.2.
  • the mass per unit area (“layer weight”) was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942. To determine the pickling rate, the cleaned sheets were weighed and then phosphated. The phosphate layer was removed in 5% chromic acid solution and the sheets were weighed again. The weight difference provides the pickling rate.
  • Table 1 Bath parameters, layer weights and pickling rates

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un procédé d'ajustement du poids de couche à des valeurs comprises entre 1 et 3,5 g/m2 lors de la phosphatation de surfaces en acier, acier galvanisé, acier galvanisé allié ainsi qu'en aluminium et ses alliages avec des solutions de phosphatation renfermant du zinc. Ledit procédé est caractérisé en ce que l'on plonge les surfaces métalliques pour une durée comprise entre une et huit minutes dans une solution de phosphatation contenant 0,5 à 2 g/l d'ions zinc, 2 à 25 g/l d'ions phosphate et 1,2 à 5 g/l d'hydroxylamine sous forme libre, ionique ou coordonnée, et présentant une teneur en acide libre comprise entre 0 et 1,5 point, ainsi qu'une température de l'ordre de 32 à 93 °C.
PCT/EP1996/004374 1995-10-18 1996-10-09 Ajustement du poids de couche dans des systemes de phosphatation acceleres a l'hydroxylamine WO1997014821A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU72879/96A AU7287996A (en) 1995-10-18 1996-10-09 Layer weight-adjustment in hydroxylamine-accelerated phosphatisation systems

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19538778A DE19538778A1 (de) 1995-10-18 1995-10-18 Schichtgewichtssteuerung bei Hydroxylamin-beschleunigten Phosphatiersystemen
DE19538778.3 1995-10-18

Publications (1)

Publication Number Publication Date
WO1997014821A1 true WO1997014821A1 (fr) 1997-04-24

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Application Number Title Priority Date Filing Date
PCT/EP1996/004374 WO1997014821A1 (fr) 1995-10-18 1996-10-09 Ajustement du poids de couche dans des systemes de phosphatation acceleres a l'hydroxylamine

Country Status (4)

Country Link
AU (1) AU7287996A (fr)
DE (1) DE19538778A1 (fr)
WO (1) WO1997014821A1 (fr)
ZA (1) ZA968768B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005047424A1 (de) * 2005-09-30 2007-04-05 Henkel Kgaa Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10204649A (ja) * 1997-01-24 1998-08-04 Nippon Parkerizing Co Ltd 金属表面のりん酸塩処理水溶液及び処理方法
US6179934B1 (en) 1997-01-24 2001-01-30 Henkel Corporation Aqueous phosphating composition and process for metal surfaces
US6720032B1 (en) 1997-09-10 2004-04-13 Henkel Kommanditgesellschaft Auf Aktien Pretreatment before painting of composite metal structures containing aluminum portions
DE19740953A1 (de) * 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
DE19905479A1 (de) * 1999-02-10 2000-08-17 Metallgesellschaft Ag Verfahren zur Phospatisierung von Zink- oder Aluminiumoberflächen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1086955A (fr) * 1952-08-28 1955-02-17 Parker Ste Continentale Perfectionnements relatifs à l'enduisage des métaux
FR1172741A (fr) * 1956-02-27 1959-02-13 Parker Ste Continentale Solution de phosphatation et procédé de revêtement à l'aide de cette solution
EP0315059A1 (fr) * 1987-10-30 1989-05-10 HENKEL CORPORATION (a Delaware corp.) Procédé et composition pour former un revêtement au phosphate de zinc
WO1993003198A1 (fr) * 1991-07-29 1993-02-18 Henkel Corporation Revetement a base de phosphate de zinc et procede correspondant
WO1994014999A1 (fr) * 1992-12-22 1994-07-07 Henkel Corporation Composition et procede de revetement de conversion de phosphate pratiquement sans nickel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1086955A (fr) * 1952-08-28 1955-02-17 Parker Ste Continentale Perfectionnements relatifs à l'enduisage des métaux
FR1172741A (fr) * 1956-02-27 1959-02-13 Parker Ste Continentale Solution de phosphatation et procédé de revêtement à l'aide de cette solution
EP0315059A1 (fr) * 1987-10-30 1989-05-10 HENKEL CORPORATION (a Delaware corp.) Procédé et composition pour former un revêtement au phosphate de zinc
WO1993003198A1 (fr) * 1991-07-29 1993-02-18 Henkel Corporation Revetement a base de phosphate de zinc et procede correspondant
WO1994014999A1 (fr) * 1992-12-22 1994-07-07 Henkel Corporation Composition et procede de revetement de conversion de phosphate pratiquement sans nickel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005047424A1 (de) * 2005-09-30 2007-04-05 Henkel Kgaa Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren

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DE19538778A1 (de) 1997-04-24
AU7287996A (en) 1997-05-07
ZA968768B (en) 1997-04-18

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